CN110511482A - A kind of ultrahigh flame-retardant, physical blowing squeeze out PP composite material and preparation method - Google Patents
A kind of ultrahigh flame-retardant, physical blowing squeeze out PP composite material and preparation method Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/14—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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Abstract
The invention discloses a kind of ultrahigh flame-retardant, physical blowings to squeeze out PP composite material and preparation method, is made by following components by weight percent: 66-87 parts of high melt strength, propylene, 2-5 parts of filling modifying agent, 0.5-2 parts of polyborosiloxane, 3-10 parts of fire retardant, 1-3 parts of fire retarding synergist, 0.5-2 parts of compatilizer, 6-12 parts of physical blowing agent, 0.1-0.3 parts of lubricant, light is agent 0.1-0.3 parts steady, 0.05-0.3 parts of nucleating agent, 0.2-0.6 parts of antioxidant.Ultrahigh flame-retardant, physical blowing extrusion PP composite material can be prepared by using raw materials such as high melt strength, propylene, polyborosiloxane (self-control), fire retardant and fire retarding synergists and in conjunction with special preparation process, the composite material apparent density after foaming is 0.04-0.1g/cm3, amount of expansion reaches 107‑109A/cm3, cell diameter reaches 30-60 microns, has 90% cell diameter up to 30-50 micron level, flame retardant property can be widely applied to the every field such as automobile, household electrical appliances, packaging up to UL-V0 grade.
Description
Technical field
The invention belongs to technical field of polymer materials more particularly to a kind of ultrahigh flame-retardant, physical blowing to squeeze out polypropylene
Composite material and preparation method.
Background technique
Polypropylene (PP) is a kind of crystalline polymer of compound with regular structure, is often white pellet or powder, is tasteless, nothing
Malicious, light thermoplastic resin.Polypropylene has the advantages that easy processing, impact strength, flexibility and electrical insulating property are good, and has
Have good chemical-resistance, auto industry, household electrical appliance, electronics, packaging, building materials and in terms of have and widely answer
With.
EPP (Expanded Polypropylene) i.e. expanded polypropylene material, it is a kind of half high knot haveing excellent performance
It is slow to become current fastest-rising novel environment friendly resistance to compression with its unique and superior performance for crystal form polymer/gas recombination material
Rush heat-barrier material.EPP product has response rate height, good heat resistance, resistance toization after very excellent antidetonation energy absorption performance, deformation
Product, oil resistivity and thermal insulation；Meanwhile light weight, article quality can be greatly reduced；In addition, EPP or a kind of environmentally friendly material
Material, it is prone to β degradation, and PP foam, convenient for recycling, environment friendly is better than other foamed materials, thus is referred to as
" green " foam.Just because of the excellent properties that it is showed, so that EPP becomes after polystyrene (EPS), polyurethane
(EPU) novel foam material of application value and market potential is had more after foamed material.The EPP of conventional method production is a kind of
Line style semicrystalline polymeric, the seldom branching of strand, molecular weight distribution relative narrower, this leads to its softening point and fusing point very
It is close.Before temperature reaches fusing point, it is not flowed substantially, and after temperature is more than fusing point, melt strength sharply declines, this molten
Body is difficult to encase gas；In addition, polypropylene, which is changed into crystalline state from molten state, can release a large amount of heat, it is solid by melt transform
It is longer the time required to body；In addition polypropylene air penetrability is high, and foamed gas is easily escaped.Therefore it is suitable for polypropylene expanded temperature range
Narrow, foaming process is difficult to control, and steep that wall rupture in foaming process, gas escape, abscess collapsing and bubble is easily caused to merge.Cause
And to obtain the PP foam material of high quality, it is crucial for improving its melt strength.
Polyborosiloxane is a kind of novel high-molecular organic material, it is the silicon oxygen bone that boron element is introduced to polysiloxanes
Polymer obtained from frame, more common organosiloxane have more excellent high temperature resistance and flame retardant property, by itself plus
Enter into polypropylene material the dispersion that can effectively assist fire retardant and fire retarding synergist, plays good flame retardant synergism.
Chinese patent (106279965 A of CN) discloses a kind of physical blowing filling anti-flaming polypropylene material and its preparation
Method, the fire retardant and fire retarding synergist content that this patent uses are high, and are injection foaming, and expansion ratio is low (after foaming
Density is in 0.68-1.13g/cm3)。
Chinese patent (102372855 A of CN) discloses a kind of supercritical method for preparing pre-foamed polypropylene, this patent is fortune
Polypropylene is made to increase melt strength processing, and pass through special prefoam work using physical blowing agent with supercritical fluid method
Skill prepares pre-foamed polypropylene material；Preparation method mainly uses PP and PE to be crosslinked, at the same by addition inorganic filler with
Elastomer increases its melting range and achievees the purpose that increase melt strength, but there are hairs that is uncontrollable, therefore preparing for degree of cross linking etc.
The homogeneity and stability of foam material abscess are a problems.
Summary of the invention
The object of the invention is to remedy the disadvantages of known techniques, a kind of ultrahigh flame-retardant is provided, physical blowing squeeze out it is poly-
Acrylic composite and preparation method, by using high melt strength, propylene, polyborosiloxane (self-control), fire retardant and fire-retardant
The raw materials such as synergist simultaneously can prepare ultrahigh flame-retardant, physical blowing extrusion PP composite material in conjunction with special preparation process,
Composite material apparent density after foaming is 0.04-0.1g/cm3, amount of expansion reaches 107-109A/cm3, cell diameter reaches
30-60 microns, there is 90% cell diameter up to 30-50 micron level, flame retardant property can be widely applied up to UL-V0 grade
To every field such as automobile, household electrical appliances, packagings.
In order to achieve the above purpose, the present invention the following technical schemes are provided:
A kind of ultrahigh flame-retardant, physical blowing squeeze out PP composite material, are made by following components by weight percent: high fondant-strength
66-87 parts of polypropylene, 2-5 parts of filling modifying agent, 0.5-2 parts of polyborosiloxane, 3-10 parts of fire retardant, 1-3 parts of fire retarding synergist,
0.5-2 parts of compatilizer, 6-12 parts of physical blowing agent, 0.1-0.3 parts of lubricant, light is agent 0.1-0.3 parts steady, nucleating agent 0.05-0.3
Part, 0.2-0.6 parts of antioxidant.
The high melt strength, propylene is one of homopolypropylene or copolymer polypropylene or more, and melt index
It is 0.1-3g/10min under the conditions of 230 DEG C, 2.16kg.
The filling modifying agent is special talcum powder, and partial size D50 is at 0.65-1.4 μm.
The polyborosiloxane is made by following components by weight percent and method:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2-5 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in
It heats, stir in heating mantle, temperature keeps 95 DEG C, 285 revs/min of mixing speed holding, then while and being slowly added to
0.009-0.015 parts of metallocene catalyst cyclopentadienyl titanium dichlorides and 0.025-0.035 parts of co-catalyst triethyl aluminums, add catalyst
It reacts 10-12 hours afterwards, heating and stirring state is constantly in reaction process, obtains polyborosiloxane intermediate；
Wherein, the time that metallocene catalyst and co-catalyst are slowly added to is 60-90 minutes, needs to lead in whole process
Enter nitrogen protection；
(2) polyborosiloxane is prepared
Then the silicon tetrachloride and excessive distilled water (such as: 1000 parts) for weighing 90-115 parts simultaneously, are slowly added to three mouthfuls
In flask, reaction 10-12 hours is carried out after adding, finally obtains hydrolysate, and gained hydrolysate carries out deionized water washing, most
Afterwards 135 DEG C at a temperature of carry out vacuum distillation removal small molecule, finally liquid polyborosiloxane；
Wherein, the time that the silicon tetrachloride in second step and excessive distilled water are slowly added to is 40-60 minutes, entire mistake
It needs to be passed through nitrogen protection in journey.
The fire retardant is one of decabromodiphenylethane or eight bromine bisphenol S ethers or more；
The fire retarding synergist is one of antimony oxide or antimony pentoxide or more.
The compatilizer is polypropylene grafted maleic anhydride.
The physical blowing agent is one of carbon dioxide or nitrogen or more.
The lubricant is one of ethylene bis stearic acid amide, zinc stearate, calcium stearate or more；
The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and phosphorous acid three
Two kinds of ester of (2,4- di-tert-butyl-phenyl) compounding and mass ratio are 1:1；
The steady agent of light is 2,2,6,6- tetramethyl -4- piperidyl stearates and 3,5- di-t-butyl -4- hydroxy benzenes first
Sour two kinds of just hexadecyl ester compounds and mass ratio is 1:1.
The nucleating agent is diphenyl methylene sorbitol ester.
A kind of ultrahigh flame-retardant as described above, physical blowing squeeze out the preparation method of PP composite material, including following
Step:
(1) by 66-87 parts of high melt strength, propylenes, 2-5 parts of filling modifying agents, 0.5-2 parts of polyborosiloxanes, 3-10 parts
Fire retardant, 1-3 part fire retarding synergist, 0.5-2 parts of compatilizers, 0.1-0.3 parts of lubricants, the steady agent of 0.1-0.3 parts of light, 0.2-0.6
Part antioxidant, 0.05-0.3 portions of nucleating agents are added in high-speed mixer and are uniformly mixed, the revolving speed 500- of high-speed mixer
The material mixed above is put into fusion plastification in double screw extruder, in double spiral shells by 1000RPM, incorporation time 6-15min
The end of bar extruder introduces 6-12 parts of physical blowing agents, and wherein the temperature of double screw extruder is 180-220 DEG C；
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm；
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, and is eventually by cutter slice, packaging
It can.
The invention has the advantages that
1, it by the present invention in that the dispersion of fire retardant and fire retarding synergist can be significantly improved with homemade polyborosiloxane, rises
To good flame retardant synergism.
2, the present invention can reach good flame retardant effect by adding a small amount of fire retardant and fire retarding synergist, in addition phase
Holding agent can obviously improve polypropylene and other fire-retardant compatibilities.
3, the present invention is conducive to improve foaming effect by the intensity that addition filling modifying agent increases melt.
4, simple production process of the present invention, suitable mass production.
Specific embodiment
Below in conjunction with specific example, technical scheme is described further:
Following embodiment is typical case of the invention, and scope of protection of the present invention is not limited thereto.Following embodiment
It is tested with the density of comparative example according to ISO 1183-1, abscess quantity and abscess-size are carried out using scanning electron microscope (SEM)
Test, flame retardant property are tested (1.6mm thickness) according to UL-94.
The main representative material used in embodiment and comparative example is as follows:
High melt strength, propylene (HMSPP):
Model: WB140HMS (melt index 0.1g/10min) producer: Borealis；
Model: K8003 (melt index 3g/10min) producer: Shanghai match section；
Plain polypropylene (PP):
Model: K7926 (melt index 26g/10min) producer: Shanghai match section；
Filling modifying agent:
Model: HTPultra5L (D50=0.65 μm) producer: Yi meter Fa ratio；
Model: HTP05 (D50=0.65 μm) producer: Yi meter Fa ratio；
Fire retardant:
Model: decabromodiphenylethane producer: Shandong sea Wang Huagong；
Model: eight bromine bisphenol S ether producers: chemical industry is won together in Shandong；
Fire retarding synergist:
Model: antimony oxide producer: Yiyang Hengchang；
Model: antimony pentoxide producer: Shanghai Jin Jin is happy；
Compatilizer:
Model: CA100 producer: French Acker Ma；
Antioxidant:
Model: 1010 producer of Hinered phenols: Yixing City angel synthesizes chemistry；
Model: 168 producer of phosphorous acid esters: Yixing City angel synthesizes chemistry；
Light stabilizer:
Model: LA-402AF producer: Japanese Ai Dike；
Nucleating agent:
Model: TMP-6 producer: Shanxi chemical research institute；
Lubricant:
Amides model: TR451 producer: U.S. STRUKTOL；
Calcium stearate model: BS-3818 producer: Huaming Thailand chemical industry；
Zinc stearate model: BS-2818 producer: Huaming Thailand chemical industry；
Magnesium stearate model: BS-5818 producer: Huaming Thailand chemical industry；
Embodiment 1
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.009
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.025 part of co-catalyst
Aluminium), it reacts 10 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 60 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 90 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 40 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 66 parts of high melt strength, propylene WB140HMS, 5 parts of filling modifying agent HTPultra5L, 2 parts of above-mentioned self-controls
Polyborosiloxane, 10 parts of flame retardant decabromodiphenylethane, 3 parts of fire retarding synergist antimony oxides, 2 parts of Compatibilizer C A100,0.3
Part lubricant TR451, the steady agent of 0.3 part of light, 0.6 part of antioxidant, 0.3 portion of nucleating agent are added in high-speed mixer and are uniformly mixed,
The material mixed above is put into double screw extruder and is melted by the revolving speed 500RPM of high-speed mixer, incorporation time 6min
Melt plasticizing, introduces 12 parts of physical blowing agent carbon dioxide in the end of double screw extruder, wherein the temperature of double screw extruder
It is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
Comparative example 1: homemade polyborosiloxane is not added
PP composite material the preparation method is as follows:
(1) by 66 parts of high melt strength, propylene WB140HMS, 5 parts of filling modifying agent HTPultra5L, 10 parts of fire retardants
Decabromodiphenylethane, 3 parts of fire retarding synergist antimony oxides, 2 parts of Compatibilizer C A100,0.3 part of lubricant TR451,0.3 part of light
Steady agent, 0.6 part of antioxidant, 0.3 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, the revolving speed of high-speed mixer
The material mixed above is put into fusion plastification in double screw extruder by 500RPM, incorporation time 6min, is squeezed in twin-screw
The end of machine introduces 12 parts of physical blowing agent carbon dioxide out, and wherein the temperature of double screw extruder is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
Comparative example 2: filling modifying agent is not added
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.009
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.025 part of co-catalyst
Aluminium), it reacts 10 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 60 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 90 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 40 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 66 parts of high melt strength, propylene WB140HMS, 2 parts of above-mentioned self-control polyborosiloxanes, 10 parts of fire retardants ten
Bromine diphenylethane, 3 parts of fire retarding synergist antimony oxides, 2 parts of Compatibilizer C A100,0.3 part of lubricant TR451,0.3 part of light are steady
Agent, 0.6 part of antioxidant, 0.3 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, the revolving speed 500RPM of high-speed mixer,
The material mixed above is put into fusion plastification in double screw extruder, in double screw extruder by incorporation time 6min
End introduces 12 parts of physical blowing agent carbon dioxide, and wherein the temperature of double screw extruder is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
Comparative example 3: compatilizer is not added
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.009
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.025 part of co-catalyst
Aluminium), it reacts 10 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 60 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 90 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 40 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 66 parts of high melt strength, propylene WB140HMS, 5 parts of filling modifying agent HTPultra5L, 2 parts of above-mentioned self-controls
Polyborosiloxane, 10 parts of flame retardant decabromodiphenylethane, 3 parts of fire retarding synergist antimony oxides, 0.3 part of lubricant TR451,
The steady agent of 0.3 part of light, 0.6 part of antioxidant, 0.3 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, and high-speed mixer turns
The material mixed above is put into fusion plastification in double screw extruder, in twin-screw by fast 500RPM, incorporation time 6min
The end of extruder introduces 12 parts of physical blowing agent carbon dioxide, and wherein the temperature of double screw extruder is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
Comparative example 4: fire retardant and fire retarding synergist is not added
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.009
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.025 part of co-catalyst
Aluminium), it reacts 10 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 60 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 90 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 40 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 66 parts of high melt strength, propylene WB140HMS, 5 parts of filling modifying agent HTPultra5L, 2 parts of above-mentioned self-controls
Polyborosiloxane, 2 parts of Compatibilizer C A100,0.3 part of lubricant TR451, the steady agent of 0.3 part of light, 0.6 part of antioxidant, 0.3 part of nucleation
Agent is added in high-speed mixer and is uniformly mixed, and the revolving speed 500RPM of high-speed mixer, incorporation time 6min will be mixed above
Material put into fusion plastification in double screw extruder, double screw extruder end introduce 12 parts of physical blowing agent dioxies
Change carbon, wherein the temperature of double screw extruder is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
Comparative example 5: plain polypropylene substitutes high melt strength, propylene
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.009
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.025 part of co-catalyst
Aluminium), it reacts 10 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 60 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 90 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 40 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 66 parts of plain polypropylene K7926,5 parts of filling modifying agent HTPultra5L, 2 parts of above-mentioned poly- borosilicate oxygen of self-control
Alkane, 10 parts of flame retardant decabromodiphenylethane, 3 parts of fire retarding synergist antimony oxides, 2 parts of Compatibilizer C A100,0.3 part of lubricant
TR451, the steady agent of 0.3 part of light, 0.6 part of antioxidant, 0.3 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, mixed at high speed
The material mixed above is put into fusion plastification in double screw extruder, In by the revolving speed 500RPM of machine, incorporation time 6min
The end of double screw extruder introduces 12 parts of physical blowing agent carbon dioxide, and wherein the temperature of double screw extruder is 180-220
℃。
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 1.
1 embodiment 1 of table and comparative example 1-5 performance
From the above table 1 as can be seen that high melt strength, propylene, self-control polyborosiloxane, fire retardant and fire retarding synergist,
Compatilizer, filling modifying agent are indispensable, lacked any of which component have to the integrality of the entire performance of material it is larger
Influence.
Embodiment 2
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 5 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in and are added
It heated in hot jacket, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and being slowly added to 0.015
(co-catalyst is triethyl group for part metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.035 part of co-catalyst
Aluminium), it reacts 12 hours (being constantly in heating and stirring state in reaction process), is obtained among polyborosiloxane after adding catalyst
Body.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 90 minutes.Need to be passed through nitrogen guarantor in whole process
Shield.
(2) polyborosiloxane is prepared
Then it weighs 115 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 12 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally 135
Vacuum distillation removal small molecule is carried out at a temperature of DEG C, finally obtains liquid polyborosiloxane.Note: silicon tetrachloride in second step and
The time that excessive distilled water is slowly added to is 60 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 87 parts of high melt strength, propylene K8003,2 parts of filling modifying agent HTP05,0.5 part of above-mentioned poly- borosilicate of self-control
Oxygen alkane, 3 parts of eight bromine bisphenol S ethers of fire retardant, 1 part of fire retarding synergist antimony pentoxide, 0.5 part of Compatibilizer C A100,0.1 part of lubrication
Agent BS-2818, the steady agent of 0.1 part of light, 0.2 part of antioxidant, 0.05 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, high speed
The material mixed above is put into double screw extruder and is melted by the revolving speed 1000RPM of mixing machine, incorporation time 15min
Plasticizing introduces 6 parts of physical blowing agent nitrogen in the end of double screw extruder, and wherein the temperature of double screw extruder is 180-
220℃。
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 2.
Embodiment 3
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 3.1 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in
It heated in heating mantle, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and be slowly added to
(co-catalyst is three second for 0.011 part of metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.027 part of co-catalyst
Base aluminium), it is reacted 10.5 hours (being constantly in heating and stirring state in reaction process) after adding catalyst, obtains polyborosiloxane
Intermediate.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 65 minutes.It needs to be passed through nitrogen in whole process
Protection.
(2) polyborosiloxane is prepared
Then it weighs 94 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10.3 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally exists
Vacuum distillation removal small molecule is carried out at a temperature of 135 DEG C, finally obtains liquid polyborosiloxane.Note: four chlorinations in second step
The time that silicon and excessive distilled water are slowly added to is 44 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 28 parts of high melt strength, propylene K8003,42 parts of high melt strength, propylene WB140HMS, 1.2 parts of fillings
Modifying agent HTPultra5L, 2 parts of filling modifying agent HTP05,0.9 part of above-mentioned self-control polyborosiloxane, 5 parts of eight bromine bis-phenols of fire retardant
S ether, 1.3 parts of fire retarding synergist antimony oxides, 0.8 part of Compatibilizer C A100,0.1 part of lubricant BS-2818,0.1 part of lubricant
BS-5818, the steady agent of 0.17 part of light, 0.29 part of antioxidant, 0.09 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, high speed
The material mixed above is put into double screw extruder and is melted by the revolving speed 675RPM of mixing machine, incorporation time 7.2min
Plasticizing introduces 7 parts of physical blowing agent carbon dioxide in the end of double screw extruder, and wherein the temperature of double screw extruder is
180-220℃。
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 2.
Embodiment 4
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 3.4 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in
It heated in heating mantle, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and be slowly added to
(co-catalyst is three second for 0.012 part of metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.029 part of co-catalyst
Base aluminium), it is reacted 10.9 hours (being constantly in heating and stirring state in reaction process) after adding catalyst, obtains polyborosiloxane
Intermediate.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 69 minutes.It needs to be passed through nitrogen in whole process
Protection.
(2) polyborosiloxane is prepared
Then it weighs 99 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 10.8 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally exists
Vacuum distillation removal small molecule is carried out at a temperature of 135 DEG C, finally obtains liquid polyborosiloxane.Note: four chlorinations in second step
The time that silicon and excessive distilled water are slowly added to is 47 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 43 parts of high melt strength, propylene K8003,29 parts of high melt strength, propylene WB140HMS, 2.2 parts of fillings
Modifying agent HTPultra5L, 1.6 parts of filling modifying agent HTP05,0.9 part of above-mentioned self-control polyborosiloxane, 7 parts of eight bromines of fire retardant are double
Phenol S ether, 1.5 parts of fire retarding synergist antimony oxides, 0.9 part of Compatibilizer C A100,0.12 part of lubricant TR451,0.1 part of lubrication
Agent BS-3818, the steady agent of 0.19 part of light, 0.37 part of antioxidant, 0.18 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, high
The material mixed above is put into double screw extruder and is melted by the revolving speed 795RPM of fast mixing machine, incorporation time 7.7min
Melt plasticizing, introduces 8 parts of physical blowing agent carbon dioxide in the end of double screw extruder, wherein the temperature of double screw extruder is
180-220℃。
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 2.
Embodiment 5
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 3.8 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in
It heated in heating mantle, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and be slowly added to
(co-catalyst is three second for 0.013 part of metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.031 part of co-catalyst
Base aluminium), it is reacted 11.4 hours (being constantly in heating and stirring state in reaction process) after adding catalyst, obtains polyborosiloxane
Intermediate.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 78 minutes.It needs to be passed through nitrogen in whole process
Protection.
(2) polyborosiloxane is prepared
Then it weighs 107 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 11.2 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally exists
Vacuum distillation removal small molecule is carried out at a temperature of 135 DEG C, finally obtains liquid polyborosiloxane.Note: four chlorinations in second step
The time that silicon and excessive distilled water are slowly added to is 52 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 43 parts of high melt strength, propylene K8003,39 parts of high melt strength, propylene WB140HMS, 2.4 parts of fillings
Modifying agent HTPultra5L, 1.6 parts of filling modifying agent HTP05,1.2 parts of above-mentioned self-control polyborosiloxanes, 8 parts of ten bromines two of fire retardant
Vinylbenzene, 2.3 parts of fire retarding synergist antimony oxides, 1.3 parts of Compatibilizer C A100,0.12 part of lubricant TR451,0.18 part of profit
Lubrication prescription BS-2818, the steady agent of 0.25 part of light, 0.48 part of antioxidant, 0.25 portion of nucleating agent are added in high-speed mixer and are uniformly mixed,
The revolving speed 850RPM of high-speed mixer, incorporation time 7.9min put into the material mixed above in double screw extruder
Fusion plastification introduces 9 parts of physical blowing agent carbon dioxide in the end of double screw extruder, wherein the temperature of double screw extruder
It is 180-220 DEG C.
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 2.
Embodiment 6
1, the preparation of polyborosiloxane:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 4.6 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in
It heated in heating mantle, stir (temperature keeps 95 DEG C, 285 revs/min of mixing speed holding), then while and be slowly added to
(co-catalyst is three second for 0.014 part of metallocene catalyst (metallocene catalyst is cyclopentadienyl titanium dichloride) and 0.034 part of co-catalyst
Base aluminium), it is reacted 11.9 hours (being constantly in heating and stirring state in reaction process) after adding catalyst, obtains polyborosiloxane
Intermediate.Note: the time that metallocene catalyst and co-catalyst are slowly added to is 87 minutes.It needs to be passed through nitrogen in whole process
Protection.
(2) polyborosiloxane is prepared
Then it weighs 112 parts of silicon tetrachloride simultaneously and excessive distilled water (such as: 1000 parts) is slowly added to three-necked flask
In, reaction 11.8 hours is carried out after adding, and finally obtains hydrolysate.Gained hydrolysate carries out deionized water washing, finally exists
Vacuum distillation removal small molecule is carried out at a temperature of 135 DEG C, finally obtains liquid polyborosiloxane.Note: four chlorinations in second step
The time that silicon and excessive distilled water are slowly added to is 57 minutes.It needs to be passed through nitrogen protection in whole process.
2, the preparation of PP composite material:
(1) by 37 parts of high melt strength, propylene K8003,46 parts of high melt strength, propylene WB140HMS, 3.4 parts of fillings
Modifying agent HTPultra5L, 1.6 parts of filling modifying agent HTP05,1.7 parts of above-mentioned self-control polyborosiloxanes, 4 parts of ten bromines two of fire retardant
Vinylbenzene, 5 parts of eight bromine bisphenol S ethers of fire retardant, 1.3 parts of fire retarding synergist antimony oxides, 1.3 parts of oxidations of fire retarding synergist five two
Antimony, 1.8 parts of Compatibilizer C A100,0.12 part of lubricant BS-3818,0.18 part of lubricant BS-2818, the steady agent of 0.28 part of light, 0.57
Part antioxidant, 0.28 portion of nucleating agent are added in high-speed mixer and are uniformly mixed, the revolving speed 960RPM of high-speed mixer, when mixing
Between 12.8min, the material mixed above is put into fusion plastification in double screw extruder, in the end of double screw extruder
6 parts of physical blowing agent carbon dioxide, 5 parts of physical blowing agent nitrogen are introduced, wherein the temperature of double screw extruder is 180-220
℃。
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, squeezed out
The die head thickness of foaming machine can be adjusted in 1.0-3.0mm.
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
Performance is shown in Table 2.
2 embodiment 2-6 performance of table
From the above table 1, table 2 as can be seen that composite material apparent density is 0.04-0.1g/cm3, amount of expansion reaches 107-
109A/cm3, cell diameter reaches 30-60 microns, has 90% cell diameter up to 30-50 micron level, flame retardant property is reachable
UL-V0 grade can be widely applied to the every field such as automobile, household electrical appliances, packaging.
Claims (10)
1. a kind of ultrahigh flame-retardant, physical blowing squeeze out PP composite material, which is characterized in that be made by following components by weight percent:
66-87 parts of high melt strength, propylene, 2-5 parts of filling modifying agent, 0.5-2 parts of polyborosiloxane, 3-10 parts of fire retardant, fire-retardant association
Agent 1-3 parts of effect, 0.5-2 parts of compatilizer, 6-12 parts of physical blowing agent, 0.1-0.3 parts of lubricant, light are agent 0.1-0.3 parts steady, are nucleated
0.05-0.3 parts of agent, 0.2-0.6 parts of antioxidant.
2. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
High melt strength, propylene is one of homopolypropylene or copolymer polypropylene or more, and melt index 230 DEG C,
It is 0.1-3g/10min under the conditions of 2.16kg.
3. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Filling modifying agent is special talcum powder, and partial size D50 is at 0.65-1.4 μm.
4. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Polyborosiloxane is made by following components by weight percent and method:
(1) polyborosiloxane intermediate is prepared
100 parts of triethoxy borine and 2-5 parts of silicon tetrachloride are weighed first in the three-necked flask of 5000ml, are placed in heating
It heats, stir in set, temperature keeps 95 DEG C, 285 revs/min of mixing speed holding, then while and being slowly added to 0.009-
0.015 part of metallocene catalyst cyclopentadienyl titanium dichloride and 0.025-0.035 parts of co-catalyst triethyl aluminums, react after adding catalyst
10-12 hours, it is constantly in heating and stirring state in reaction process, obtains polyborosiloxane intermediate；
Wherein, the time that metallocene catalyst and co-catalyst are slowly added to is 60-90 minutes, needs to be passed through nitrogen in whole process
Gas shielded；
(2) polyborosiloxane is prepared
Then the silicon tetrachloride and excessive distilled water for weighing 90-115 parts simultaneously, are slowly added in three-necked flask, add laggard
Row reaction 10-12 hours finally obtains hydrolysate, and gained hydrolysate carries out deionized water washing, finally in 135 DEG C of temperature
Under carry out vacuum distillation removal small molecule, finally liquid polyborosiloxane；
Wherein, the time that the silicon tetrachloride in second step and excessive distilled water are slowly added to is 40-60 minutes, in whole process
It needs to be passed through nitrogen protection.
5. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Fire retardant is one of decabromodiphenylethane or eight bromine bisphenol S ethers or more；The fire retarding synergist be antimony oxide or
One of antimony pentoxide or more.
6. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Compatilizer is polypropylene grafted maleic anhydride.
7. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Physical blowing agent is one of carbon dioxide or nitrogen or more.
8. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Lubricant is one of ethylene bis stearic acid amide, zinc stearate, calcium stearate or more；The antioxidant be four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and two kinds of ester of phosphorous acid three (2,4- di-tert-butyl-phenyl) compounding and
Mass ratio is 1:1；The steady agent of light is 2,2,6,6- tetramethyl -4- piperidyl stearates and 3,5- di-t-butyl -4- hydroxyl
Two kinds of the positive hexadecyl ester of benzoic acid compoundings and mass ratio are 1:1.
9. ultrahigh flame-retardant according to claim 1, physical blowing squeeze out PP composite material, which is characterized in that described
Nucleating agent is diphenyl methylene sorbitol ester.
10. a kind of preparation for squeezing out PP composite material such as the described in any item ultrahigh flame-retardants of claim 1-9, physical blowing
Method, which comprises the following steps:
(1) by 66-87 parts of high melt strength, propylenes, 2-5 parts of filling modifying agents, 0.5-2 parts of polyborosiloxanes, 3-10 parts it is fire-retardant
Agent, 1-3 parts of fire retarding synergists, 0.5-2 parts of compatilizers, 0.1-0.3 parts of lubricants, the steady agent of 0.1-0.3 parts of light, 0.2-0.6 parts it is anti-
Oxygen agent, 0.05-0.3 portions of nucleating agents are added in high-speed mixer and are uniformly mixed, the revolving speed 500-1000RPM of high-speed mixer,
The material mixed above is put into fusion plastification in double screw extruder, in double screw extruder by incorporation time 6-15min
End introduce 6-12 part physical blowing agents, wherein the temperature of double screw extruder be 180-220 DEG C；
(2) melt above containing physical blowing agent is added in special extrusion foaming machine and carries out physical blowing, extrusion foaming
The die head thickness of machine can be adjusted in 1.0-3.0mm；
(3) sheet material to foam enters three-roller after coming out from extrusion foaming machine and transmits, eventually by cutter slice, packaging.
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